Epoxy-modified polyolefin wax, process for preparation thereof and thermosetting resinous composition comprising said wax

ABSTRACT

An epoxy-modified polyolefin wax, which consists of a low-molecular-weight polyolefin grafted, copolymerized and modified with an epoxy group-containing, ethylenically unsaturated compound and has a number average molecular weight of from 600 to 10,000 and an epoxy equivalent of from 200 to 100,000, is disclosed. 
     This epoxy-modified polyolefin wax is very valuable as a modifier for improving brittleness or adhesion (adhesiveness) in various resins, especially thermosetting resins.

This is a division, of Application Ser. No. 967,905, filed Dec. 11,1978, now U.S. Pat. No. 4,245,061.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to a novel epoxy-modified polyolefin wax, aprocess for the preparation of this wax and a thermosetting resinouscomposition comprising this wax as a modifier.

(2) Description of the Prior Art

Polyolefin waxes such as polyethylene waxes have heretofore been broadlyused as lubricants, parting agents and the like. It is known that aproduct formed by introducing polar groups into a polyolefin wax byoxidizing treatment or grafting treatment with an ethylenicallyunsaturated carboxylic acid or its anhydride such as maleic anhydride isincorporated into a thermosetting resin paint for improving flowcharacteristics or levelling properties.

However, most of known polyolefin waxes or acid-modified polyolefinwaxes are poor in compatibility with base resins and their reactivitywith base resins are low. Accordingly, resinous compositions formed byincorporating these polyolefin waxes or acid-modified polyolefin waxesinto base resins are still insufficient in mechanical and chemicalproperties.

SUMMARY OF THE INVENTION

We found that a low-molecular-weight polyolefin wax modified and graftedwith an epoxy group-containing, ethylenically unsaturated monomer has anexcellent compatibility with resins used as paint, adhesives, moldingmaterials and the like, and that when this epoxy-modified polyolefin waxis incorporated into these resins, mechanical properties such as shockresistance, heat resistance, adhesion and adhesiveness and chemicalproperties such as water resistance, oxidation resistance and chemicalresistance can be remarkably improved in the resulting resinouscompositions.

It is therefore a primary object of this invention to provide a novelepoxy-modified polyolfein wax which has an excellent compatibility withvarious resins.

Another object of this invention is to provide an epoxy-modifiedpolyolefin wax which is very valuable as a modifier to be incorporatedin various resins for improving mechanical properties such as shockresistance, heat resistance, adhersion and adhesiveness and chemicalproperties such as water resistance, oxidation resistance and chemicalresistance.

Still another object of this invention to provide a novel resinouscomposition especially valuable as a paint, an adhesive, a moldingmaterial or the like, which comprises a thermosetting resin and anepoxy-modified polyolfein wax.

In accordance with one aspect of this invention, there is provided anepoxy-modified polyolefin wax, which consists of a low-molecular-weightpolyolefin grafted, copolymerized and modified with an epoxygroup-containing, ethylenically unsaturated compound and has a numberaverage molecular weight of from 600 to 10,000 and an epoxy equivalentof from 200 to 100,000.

In accordance with another aspect of this invention, there is provided athermosetting resinous composition comprising a thermosetting resin and0.5 to 70 parts by weight, per 100 parts by weight of said thermosettingresin, of an epoxy-modified polyolefin wax consisting of alow-molecular-weight polyolefin grafted, copolymerized and modified withan epoxy group-containing, ethylenically unsaturated compound and havinga number average molecular weight of from 600 to 10,000 and an epoxyequivalent of from 200 to 100,000.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The epoxy-modified polyolefin wax of this invention should have a numberaverage molecular weight of from 600 to 10,000, preferably from 700 to6,000, especially preferably from 1,000 to 4,000, and an epoxyequivalent of from 200 to 100,000, preferably from 200 to 10,000,especially preferably from 200 to 6,000. In order to improve thecompatibility of the epoxy-modified polyolefin wax with various resinsand mechanical and chemical properties of the resulting resinouscompositions, it is very important that these requirements of the numberaverage molecular weight and epoxy equivalent should be satisfied.

More specifically, epoxy-modified olefin resins having a number averagemolecular weight exceeding the above range, for example, epoxy-modifiedolefin resins disclosed in Japanese Patent Publication No. 31726/77 andJapanese Patent Application Laid-Open Specification No. 551/76. are verypoor in the compatibility with other resins such as epoxy resins.Further, resinous compositions including such high-molecular-weightepoxy-modified olefin resin have a defect that the viscosity isdrastically increased in the molten state or in the form of a solutionand their processability as paints, adhesives or molding materials isreduced. Moreover, these resinous compositions are still insufficient inappearance characteristics, mechanical properties such as shockresistance and chemical properties such as water resistance. When thenumber average molecular weight is too low and below the above range,mechanical properties such as adhesiveness and shock resistance andchemical properties such s water resistance, oxidation resistance andchemical resistance are degraded in resinous compositions including suchepoxy-modified polyolefin wax. In the epoxy-modified polyolefin wax ofthis invention, the epoxy equivalent is closely related to thereactivity and compatibility with a thermosetting resin in which theepoxy-modified polyolefin wax is incorporated. When an epoxy-modifiedpolyolefin wax having an epoxy equivalent included within the aboverange is employed, preferred reactivity and compatibility can beattained in combination.

An epoxy-modified polyolefin wax especially suitable for attaining theobjects of this invention has a haze less than 3.1%, especially lessthan 3.0%, in the molten state. The haze referred to in the instantspecification and claims is one determined by melting a 2/8 blend ofsample/Paraffin (melting point=48°-50° C.) at 180° C., casting the melton a heated measurement cell and performing the measurement according toASTM D-1003-53.

The above-mentioned haze is closely related to the homogeneousness ofgrafting of the epoxy group-containing, ethylenically unsaturatedcompound to the polyolefin wax trunk polymer. More specifically, anepoxy-modified polyolefin wax in which the epoxy group-containing,ethylenically unsaturated compound is not homogeneously grafted to thetrunk of the polyolefin wax but molecules of such saturated compound arepolymerized with one another is insufficient in the transparency in themolten state and has an opaque appearance. Further, such modifiedpolyolefin wax is poor in the compatibility with various resins andresinous compositions including such modified polyolefin wax areinsufficient in the adhesiveness, adhesion and other properties. Incontrast, an epoxy-modified polyolefin wax having the transmittance andhaze in the above-mentioned ranges is excellent in the compatibilitywith various resins and high improvements of the above-mentionedproperties can be attained by the use of such epoxy-modified polyolefinwax.

The epoxy-modified polyolefin wax of this invention is prepared bygraft-copolymerizing an epoxy group-containing, ethylenicallyunsaturated compound to a low-molecular-weight polyolefin wax.Ordinarily, the epoxy-modified polyolefin wax is prepared by grafting,copolymerizing and modifying an unmodified low-molecular-weightpolyolefin wax having a number average molecular weight of 400 to 9,000,preferably from 600 to 5,000, with an epoxy group-containing,ethylenically unsaturated compound in the presence or absence of aradical initiator in the state dissolved in a solvent or in the moltenstate.

As the starting unmodified low-molecular-weight polyolefin wax, therecan be mentioned, for example, olefin homopolymers such as polyethylene,polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polybutadiene andpolyisoprene, and olefin copolymers such as ethylene/propylenecopolymers, ethylene/1-butene copolymers, ethylene/4-methyl-1-pentenecopolymers, ethylene/butadiene copolymers, ethylene/vinyl acetatecopolymers, propylene/ethylene copolymers, propylene/1-butenecopolymers, propylene/4-methyl-1-pentene copolymers andethylene/propylene/diene copolymers, each having a number averagemolecular weight included within the above-mentioned range. Among thesestarting unmodified low-molecular-weight polyolefin waxes, there arepreferably employed low-molecular-weight polyolefin waxes having anumber average molecular weight included within the above-mentionedrange and an ethylene content of at least 70 mole % andlow-molecular-weight polypropylene waxes having a number averagemolecular weight included within the above-mentioned range.

Methods for preparing these polyolefin waxes are known. For example,they can be prepared by a process for thermally decomposing ahigh-molecular-weight polyethylene or polypropylene or according to theFisher Tropsh synthesis process. Further, they may be prepared bypolymerizing ethylene or propylene is the presence of a Ziegler catalystand a molecular weight modifier such as hydrogen.

In this invention, as the epoxy group-containing, ethylenicallyunsaturated compound, there can be used compounds having in the moleculeat least one graft-copolymerizable unsaturated carbon-to-carbon bond andat least one epoxy group. For example, there can be mentioned glycidylesters of unsaturated monocarboxylic acids such as glycidyl acrylate,glycidyl methacrylate and glycidyl p-styrylcarboxylate, mono- andpoly-glycidyl esters of unsaturated polycarboxylic acids such as maleicacid, itaconic acid, citraconic acid, butene-tricarboxylic acid,endo-cis-bicyclo[2,2,1]hepto-5-ene-2,3-dicarboxylic acid andendo-cis-bicyclo[2,2,1]hepto-5-ene-2-methyl-2,3-dicarboxylic acid,unsaturated glycidyl ethers such as allyl glycidyl ether, 2-methylallylglycidyl ether, o-allylphenyl glycidyl ether, m-allylphenyl glycidylether, p-allylphenyl glycidyl ether, isopropenylphenyl glycidyl ether,o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether andp-vinylphenyl glycidyl ether, and 2-(o-vinylphenyl)ethylene oxide,2-(p-vinylphenyl)ethylene oxide, 2-(o-vinylphenyl)propylene oxide,2-(p-vinylphenyl)-propylene oxide, 2-(o-allylphenyl)ethylene oxide,2-(p-allylphenyl)ethylene oxide, 2-(o-allylphenyl)propylene oxide,2-(p-allylphenyl)propylene oxide, p-glycidylstyrene, 3,4-epoxy-1-butene,3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene,3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexenemonoxide and allyl-2,3-epoxycyclopentyl ether.

Among these epoxy group-containing, ethylenically unsaturated compounds,there are preferably employed compounds represented by the followingformula: ##STR1## wherein R stands for a monovalent hydrocarbon groupcontaining a polymerizable ethylenically unsaturated bond.

Especially preferred examples of the compound represented by the formula(1) include allyl glycidyl ether, 2-methylallyl glycidyl ether,isopropenylphenyl glycidyl ether and allylphenyl glycidyl ether.

Another preferred class of epoxy group-containing, ethylenicallyunsaturated compounds are those represented by the following formula:##STR2## wherein R stands for a monovalent hydrocarbon group containinga polymerizable ethylenically unsaturated bond, and R' stands for ahydrogen atom or an alkyl group having up to 4 carbon atoms.

Among compounds represented by the formula (2), 2-(allylphenyl)ethyleneoxide is especially preferred.

Such epoxy group-containing, ethylenically unsaturated compound isreacted with the polyolefin wax in such an amount that theabove-mentioned requirement of the epoxy equivalent should be satisfied.

In practising the graft polymerization, it is desired that a homopolymerof the epoxy group-containing, ethylenically unsaturated compound willnot be formed by polymerization of molecules of such unsaturatedcompound. Compounds represented by the above formula (1) or (2) areespecially suitable for attaining this object. Further, this object canbe conveniently attained by carrying out the graft polymerization whilefeeding continuously or intermittently the unsaturated epoxy compound ata speed of 10⁻⁵ to 10⁻² mole/hr, especially 4×10⁻⁵ to 10⁻³ mole/hr. pergram of the starting low-molecular-weight polyolefin wax.

The graft polymerization is carried out in an inert atmosphere at atemperature of 80° to 200° C., especially 120° to 180° C., underagitation or kneading under such condition that the starting wax isflowable. For example, when the starting wax has a melting point higherthan 80° C., the starting wax is heated at a temperature higher themelting point thereof, or a hydrocarbon other than an alkyl aromatichydrocarbon is added as a solvent so as to lower the pour point. In thisinvention, it is preferred that the graft polymerization for obtainingthe epoxy-modified polyolefin wax be carried out substantially in theabsence of the solvent. Namely, it is preferred that the amount of thesolvent be smaller than 30% by weight based on the starting polyolefinwax. It is most preferred that the graft polymerization be carried outin the absence of the solvent in the state where the starting polyolefinwax is molten.

The unreacted unsaturated epoxy monomer, oligmers thereof, the radicalinitiator and decomposition products thereof may be removed from thereaction mixture obtained according to the above-mentioned process, ifdesired. For this purpose, there may be adopted a method comprisingmaintaining a reduced pressure in a reaction vessel, a method comprisingcontinuously feeding the reaction mixture into a film evaporatormaintained under a reduced pressure, a method comprising dissolving thereaction mixture in a solvent such as acetone, methylethyl ketone.methylisobutyl ketone, dioxane, methyl alcohol, ethyl alcohol, isopropylalcohol, an acetic acid ester, chloroform or benzene and thenprecipitating the reaction product, and a method comprising dippingreaction mixture in water and recovering the washed reaction product.Thus, the intended epoxy-modified polyolefin wax is obtained.

The epoxy-modified polyolefin wax of this invention has several novelproperties that are not observed in known polyolefin waxes. Namely, theepoxy-modified polyolefin wax of this invention retain propertiesinherent of waxes and has an excellent adhesiveness of various metalssuch as steel, aluminum, copper, zinc and tin-plated steel and also topolyester resins such as polyethylene terephthalate and polybutyleneterephthalate and polyamide resins such as various nylons. Therefore,when the epoxy-modified polyolefin wax is incorporated into a paint oradhesive. the adhesion or adhesiveness to a substrate can be remarkablyimproved.

Further, the epoxy-modified polyolefin wax of this invention is veryeffective as a dispersant or dispersing assistant for improving thedispersibility of a pigment, a filler, an aggregate or the like into aresin, a paint, an ink vehicle or the like.

Still further, the epoxy-modified polyolfein wax of this invention isvery excellent in compatibility with various resins, especiallythermosetting resins, and when the epoxy-modified polyolefin wax of thisinvention is incorporated into such resins, the coating property,processability and adaptability to various operations can be remarkablyimproved and simultaneously, mechanical properties such as brittlenessand chemical properties can be prominently improved in paints, adhesivesand molding materials.

The epoxy-modified polyolefin wax of this invention can be incorporatedinto a thermosetting resin in an amount of 0.5 to 70 parts by weight,especially 0.5 to 50 parts by weight, per 100 parts by weight of thethermosetting resin.

The kind of the thermosetting resin in which the epoxy-modifiedpolyolefin wax of this invention is incorporated is not particularlycritical, but the epoxy-modified polyolefin wax of this inventionpreferably is incorporated into at least one thermosetting resinselected from the group consisting of phenol-formaldehyde resins.melamine-formaldehyde resins, urea-formaldehyde resins, urethane resins,unsaturated polyester resins and epoxy resins. As the most preferredthermosetting resin for attaining the objects of this invention, therecan be mentioned epoxy resins and a mixture of an epoxy resin with otherthermosetting resin exemplified above.

Epoxy resins have heretofore been broadly used in the fields ofadhesives, paints and surface-protecting coating agents. Epoxy resinsare excellent in the adhesiveness to metals, woods and other substrates,but since they are generally poor in the shock resistance, cracks areformed under shocks during use or peeling is readily caused.

When the epoxy-modified polyolefin wax of this invention is incorporatedinto epoxy resins. The shock resistance can be improved withoutdegradation of excellent adhesiveness inherent of epoxy resins andsimultaneously, chemical properties such as water resistance can befurther improved.

Versatile and ordinary epoxy resins consisting of compounds containingin the molecule at least two epoxy groups can be used. Of course,epoxy-modified low-molecular-weight polyolefins such as those of thisinvention and epoxy-containing polymers having a polyolefin skeleton,such as epoxy-containing olefin polymers obtained by directlycopolymerizing epoxy group-containing unsaturated compounds such asmentioned above in polymerizing olefins such as ethylene are excludedfrom the epoxy resins that can be used in this invention. As specificexamples of the epoxy resin that can be used in this invention, therecan be mentioned epoxy resins consisting of glycidyl ethers ofpolyphenols such as bisphenol A, bisphenol F and1,1,2,2-tetrakis(4'-hydroxyphenyl)ethane, epoxy resins consisting ofglycidyl ethers of polyhydric phenols such as catechol, resorcinol,hydroquinone and phloroglucinol, epoxy resins consisting of glycidylethers of polyhydric alcohols such as ethylene glycol, butane diol,glycerol, erythritol and polyoxyalkylene glycol, novolak type epoxyresins, cyclic aliphatic epoxy resins such as vinylcyclohexene dioxide,limonene dioxide and dicyclopentadiene dioxide, epoxy resins consistingof polyglycidyl esters of condensates of esters of polycarboxylic acidssuch as phthalic acid and cyclohexane-1,2-dicarboxylic acid, andpolyglycidyl amine type epoxy resins.

Among these epoxy resins, in this invention, there are preferably usedepoxy resins consisting of a condensate of a polyfunctional activehydrogen-containing compound with an epihalohydrin, especially epoxyresins consisting of a glycidyl ether of a polyphenol such as bisphenolA or bisphenol F and a novolak type epoxy resin.

A curing agent or a curing promotor is incorporated into thethermosetting resinous composition of this invention according to need.Further, known additives such as a filler, a pigment, a stabilizer, athixotropic agent, a flow modifier and a dispersant may be incorporatedaccording to known recipes.

For example, when an epoxy resin is used as the thermosetting resin, allthe compounds known as curing agents for epoxy resins may be used as thecuring agent. As the curing agent that can be used in this invention,there can be mentioned, for example, linear aliphatic polyamines such asdiethylene triamine, triethylene tetramine, tetraethylene pentamine,dipropylene diamine and diethylaminopropylamine, cyclic aliphaticpolyamines, aliphatic polyamine adducts, ketoimine, modified aliphaticamines, aromatic amines, aromatic modified amines, tertiary amine typecuring agents, mercaptan type curing agents, acid anhydride type curingagents, copolymers containing an acid anhydride group such asethylene/maleic anhydride copolymers, compounds containing a phenolichydroxyl group such as precondensates of phenolic resins, and othercuring compounds such as dicyandiamide, melamine and boron trifluoridecomplexes. Among these curing agents, there are preferably employeddicyandiamide, an aromatic polyamine such as diaminodiphenylmethane anda boron trifluoride-amine complex.

An acid curing agent such as phosphoric acid can be used for a resoltype phenol-formaldehyde resin, and a curing agent such as hexamethylenetetramine can be used for a novolak type phenol formaldehyde resin.

For incorporation of the epoxy-modified polyolefin wax into thethermosetting resin, there may be adopted a method in which powders ofboth the components are dryblended, a method in which both thecomponents are mixed in the solution state and a method in which boththe components are kneaded in the molten state. In each of thesemethods, an excellent adaptability to the mixing operation can beattained.

The thermosetting resinous composition of this invention can be used inthe fields of paints, surface-coating agents, adhesives and moldingmaterials. For example, for application of the thermosetting resinouscomposition of this invention, there may be adopted an electrostaticcoating method, a fluidized bed dip coating method, a press moldingmethod, an extrusion molding method, an injection molding method, acasting method, an impregnation method, a solution coating method andthe like.

As pointed out hereinbefore, the epoxy-modified polyolefin wax of thisinvention is excellent as a modifier for thermosetting resins. Themodified wax of this invention is excellent also in the compatibilitywith thermoplastic resins such as polyvinyl chloride, polyethylene,polypropylene, ethylene/propylene copolymers and other polyolefins.Accordingly, when the epoxy-modified polyolefin wax of this invention isincorporated into a polyolefin in an amount of 0.5 to 50% by weightbased on the polyolefin, the stress crack resistance, adhesiveness andreactivity of the polyolefin can be improved. When the epoxy-modifiedpolyolefin wax of this invention is incorporated in a vinyl chlorideresin, it exerts excellent properties as the lubricant and stabilizer ofthe vinyl chloride resin. Still further, the epoxy-modified polyolefinwax of this invention can be effectively used for a road-surfacingpaint. For example, when the epoxy-modified polyolefin wax of thisinvention is incorporated into a hot-melt type road-surfacing paintcomprising a binder resin such as a hydrocarbon resin, a pigment and anaggregate in an amount of 0.01 to 20 parts by weight per 100 parts byweight of the binder resin, the effect of preventing sedimentation andseparation of the aggregate in the paint can be remarkably enhanced, andthe operation adaptability of the paint can be remarkably improved.

This invention will now be described in detail by reference to thefollowing Examples that by no means limit the scope of the invention.

EXAMPLE 1 Preparation of Epoxy-Modified Wax:

Ethylene was polymerized at 180° C. in hexane as the solvent in thepresence of hydrogen by using a catalyst consisting of titaniumtetrachloride and triethyl aluminum supported on anhydrous magnesiumchloride, and volatile substances were removed from the reaction mixtureto recover a linear polyethylene wax having a number average molecularweight of 1250, a density of 0.97 and a melt viscosity of 70 cps (asmeasured at 140° C.) and containing 0.50 internal double bond per 1000carbon atoms. Then, 300 g of the so prepared wax was charged in a glassvessel having a capacity of 1 liter and equipped with a stirring rod,and externally heated by an oil bath to melt the wax. At 160° C.,nitrogen gas was blown into the vessel from the bottom thereof for 30minutes at a rate of 40 l/hr to substitute the atmosphere in the vesselby nitrogen. Then, at a temperature of 160° C. and under agitation at500 rpm. 54.8 g of allyl glycidyl ether and 12.0 g of di-tert-butylperoxide were fed into the vessel from different conduits for 8 hours atrates of 2.0×10⁻⁴ mole/g.hr and 0.34×10⁻⁴ mole/g.hr, respectively.

After completion of feeding of allyl glycidyl ether and di-tert-butylperoxide, reaction was further conducted for 1 hour. After completion ofthe reaction, the reaction mixture was maintained at a temperature of160° C. and a pressure of 5 mmHg under agitation at 500 rpm for 2 hoursto remove volatile substances such as unreacted allyl glycidyl ether anddecomposition products of di-tert-butyl peroxide and recover ahomogeneous transparent melt.

The so formed melt was transferred onto a porcelain dish and cooled andsolidified. The resulting solid was pulverized by an appropriatepulverizer to obtain a lightyellow powdery modified polyethylene wax.

The so obtained modified polyethylene wax was purified by extractionwith acetone and it was then subjected to infrared absorption spectramanalysis and oxygen analysis. It was found that the allyl glycidyl ethercontent in the modified polyethylene wax 10.6% by weight (0.930milligram equivalent/g) and that the modified polyethylene wax had anumber average molecular weight of 1700 and a density of 0.97.

Thermosetting Resinous Composition:

To a mixture of 150 g of a bisphenol type epoxy resin (EPOMIX® R-304having an epoxy equivalent of 875 to 1000 and a softening point of 93°to 140° C.; product of M.B.I. Epoxy Corp.) and 50 g of a phenol typeepoxy resin (EPOMIX® R-301 having an epoxy equivalent of 450 to 525 anda softening point of 65° to 75° C.; product of M.P.I. Epoxy Corp.) wasadded 8.8 g of a dicyandiamide type curing agent (DX-108® manufacturedby Shell Chemical Co.), and 20 g of the allyl glycidyl ether-modifiedpolyethylene wax prepared according to the above-mentioned method wasadded to the mixture. The mixture was roll-blended at 130° C. for 15minutes and then pulverized to obtain a thermosetting resinouscomposition. The composition was heated and cured at 180° C. under apressure of 100 Kg/cm² for 30 minutes. The water absorption, heatdistortion temperature and flexural strength of the so formed curedmolded product were measured to obtain results shown in Table 1.

EXAMPLES 2 AND 3 AND COMPARATIVE EXAMPLES 1 TO 3 Preparation ofEpoxy-Modified Polyolefin Wax:

The reaction was carried out in the same manner as in Example 1 exceptthat a linear polyethylene wax having a number average molecular weightof 2300, a density of 0.97 and a melt viscosity of 550 cps (as measuredat 140° C.) and containing 0.50 internal double bond per 1000 carbonatoms was used instead of the linear polyethylene wax used in Example 1.A homogeneous transparent melt was obtained (Example 2).

The allyl glycidyl ether content in the so obtained modified wax 6.5% byweight (0.570 milligram equivalent/g) and the modified wax had a numberaverage molecular weight of 3200 and a density of 0.97.

The reaction was carried out in the same manner as in Example 1 exceptthat 91.2 g of p-isopropenylphenyl glycidyl ether was used instead ofthe allyl glycidyl ether used in Example 1. A homogeneous transparentmelt was obtained (Example 3).

The p-isopropenylphenyl glycidyl ether content in the so obtainedmodified wax was 8.7% by weight (0.763 milligram equivalent/g), and themodified wax had a number average molecular weight of 2000 and a densityof 0.97. Thermosetting Resinous Composition:

Thermosetting resinous compositions and cured molded products wereprepared under the same conditions as in Example 1 except that the allylglycidyl ether-modified polyethylene wax prepared above (Example 2) orthe p-isopropenylphenyl glycidyl-modified polyethylene wax preparedabove (Example 3) was used instead of the allyl glycidyl ether-modifiedpolyethylene wax used in Example 1.

For comparison, the above procedures were repeated by using apolyethylene wax having no polar group (number average molecularweight=1250, density=0.97) (Comparative Example 1) or an oxidizedpolyethylene wax (acid value=27.2, number average molecular weight=1500and density=0.98) (Comparative Example 2) instead of the allyl glycidylether-modified polyethylene wax used in Example 1 or without using anymodified polyethylene wax (Comparative Example 3).

The water absorption, heat distortion temperature and flexural strengthof each of these five cured molded products were measured to obtainresults shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                 Example Example                                                                             Example                                                                             Comparative                                                                          Comparative                                                                          Comparative                                 1       2     3     Example 1                                                                            Example 2                                                                            Example 3                      __________________________________________________________________________    Thermosetting Composition                                                     Amounts (parts by weight) of Epoxy Resins                                     R-304®     150   150    150   150   150     150                           R-301®     50    50    50    50     50     50                             Modified Low-Molecular-Weight Polyolefin                                      Kind           allyl gly-                                                                          allyl gly-                                                                          isoprope-                                                                           unmodified                                                                           oxidized                                                                             not added                                     cidyl ether-                                                                        cidyl ether-                                                                        nylphenyl                                                                           polyethy-                                                                            polyethy-                                            grafted                                                                             grafted                                                                             glycidyl                                                                            lene wax                                                                             lene wax                                             polyethyl-                                                                          polyethyl-                                                                          ether-                                                            ene wax                                                                             ene wax                                                                             grafted                                                                       polyethy-                                                                     lene wax                                           Amounts (parts 20    20    20    20     20     0                              by weight)                                                                    Number Average Mole-                                                                         1700  3200  2000  1250   1500   --                             cular Weight 1                                                                Epoxy equivalent                                                                             1080  1750  2180  0      0      0                              Haze (%)       1.7   1.6   1.6                                                Amount (parts by weight)                                                                     8.8   8.8   8.8   8.8    8.8    8.8                            of Curing Agent (DX-108)                                                      Properties of Heat-Cured Molded Product                                       Water absorption (%) 2                                                                       0.16  0.19  0.18  0.26   0.28   0.32                           Heat Distortion Tem-                                                          perature (°C.) 3                                                                      88.0  87.0  88.0  67.5   72.0   82.0                           Flexural Strength                                                             (Kg/cm.sup.2) 4                                                                              840   820   840   510    800    1100                           __________________________________________________________________________     Note                                                                          1 The number average molecular weight was measured according to the           obulliometer method.                                                          2 The water absorption was measured according to the method of JIS K6911      52-6.                                                                         3 The heat distortion temperature was measured according to the method of     ASTM D648 under load of 264 psi.                                              4 The flexural strength was determined according to the method of ASTM        D790.                                                                    

EXAMPLE 4

An allyl glycidyl ether-grafted modified wax having an allyl glycidylether content of 2.7% by weight (0.23 milligram equivalent/g) and anumber average molecular weight of 3400 was prepared in the same manneras in Example 1 except that a propylene/ethylene copolymer wax (Viscol®550P manufactured by Sanyo Kasei K. K.) was used as the startingpolyolefin wax. Then, 20 g of the so obtained modified wax was added toa mixture of 150 g of the above-mentioned EPOMIK® R-304, 50 g of theabovementioned EPOMIK® R-301 and 20 g of an aliphatic epoxy resin(EPOMIK® R-098 having an epoxy equivalent of 148 to 156; product ofM.P.I. Epoxy Corp.), and in the same manner as described in Example 1, athermosetting resinous composition was prepared from this mixture. Then,the composition was heated and cured at 180° C. under a pressure of 100Kg/cm² for 30 minutes, and the properties of the cured molded productwere measured. It was found that the product had a water absorption of0.21%, a heat distortion temperature of 86.0° C. and a flexural strengthof 700 Kg/cm².

EXAMPLE 5

Ethylene was polymerized at 180° C. in hexane as a solvent in thepresence of hydrogen by using a catalyst consisting of titaniumtetrachloride and triethyl aluminum supported on anhydrous magnesiumchloride and volatile substances were removed from the reaction mixtureto obtain a linear polyethylene wax having a number average molecularweight of 1250, a density of 0.970 and a melt viscosity of 550 cps (asmeasured at 140° C.) and containing 0.50 internal double bond per 1000carbon atoms. Then, 300 g of the wax was charged in a glass vesselhaving a capacity of 1 liter and equipped with a stirring rod. Thevessel was externally heated on an oil bath to melt the wax and nitrogengas was blown into the vessel from the bottom thereof at a flow rate ofabout 40 l/hr for 30 minutes to replace the atmosphere by nitrogen. At160° C. under agitation, 54.8 g of allyl glycidyl ether and 12.0 g ofdi-tert-butyl peroxide were fed into the vessel from different conduitsfor 8 hours at feed rates of 2.0×10⁻⁴ mole/g.hr and 0.34×10⁻⁴ mole/g.hr,respectively. After completion of feeding of allyl glycidyl ether anddi-tert-butyl peroxide, the reaction was further conducted for 1 hour.After completion of the reaction, the reaction temperature wasmaintained at 160° C. under a pressure of 5 mmHg for 2 hours to removevolatile substances such as unreacted allyl glycidyl ether anddecomposition products of the peroxide and obtain a homogeneoustransparent melt. The melt was transferred onto a porcelain dish andcooled and solidified. The solid was pulverized by an appropriatepulverizer to obtain a light-yellow powdery modified polyethylene wax.

The modified polyethylene wax was purified by extraction with acetoneand the purified product was subjected to infrared absorption spectrumanalysis, carbon₁₃ nuclear magnetic resonance spectrum analysis andoxygen analysis. It was found that the epoxy content in the modified waxwas 1.06×10⁻³ gram equivalent per g of the modified polyethylene wax,and that the epoxy monomer was introduced into the polyethylene chain inthe monomolecular form and the epoxy group of the epoxy monomer was notsubstantially ring-opened. It also was found that modified polyethylenewax had a haze of 1.8%, a number average molecular weight of 1800, adensity of 0.970 and a melt viscosity of 268 cps (as measured at 140°C.).

In a glass vessel having a capacity of 500 ml. 0.5 g of the so preparedcrude modified polyethylene wax, 4.5 g of a bisphenol A type epoxy resin(EPOMIK® R-301 manufactured by M.P.I. Epoxy Corp.), 0.5 g ofdiaminodiphenylmethane and 100 g of methylisobutyl ketone were mixed,and the temperature wax elevated to 120° C. and immediately, the mixturewas cooled to form a dispersion. The dispersion was coated on adegreased steel plate having a thickness of 0.8 mm by a bar coater (No.22) and baked at 180° C. for 10 minutes to form a resin layer having athickness of 5 μm. Then, a powdery polyethylene (NEOZEX® 25100manufactured by Mitsui Petrochemical, Ltd; melt index=10) waselectrostatically coated on the resin layer and baked at 200° C. for 15minutes to obtain a coating resin layer a thickness of 150 μm. Then, thecoated steel plate was subjected to the peel test at room temperature(25° C.) under conditions of a peel angle of 180° and a pulling speed of50 mm/min. The peel strength was 2 Kg/cm and the coating resin layer wastightly bonded to the steel plate.

EXAMPLES 6 TO 8

Homogeneous transparent metls were prepared under the same conditions asin Example 5 except that a linear polyethylene wax having a numberaverage molecular weight of 2300, a density of 0.970 and a meltviscosity of 70 cps (as measured at 140° C.) and containing 0.50internal double bond per 1000 carbon atoms (Example 6) or a branchedpolyethylene wax having a number average molecular weight of 1250, adensity of 0.920 and a melt viscosity of 70 cps (as measured at 140° C.)and containing 20 methyl groups and 0.50 internal double bond per 1000carbon atoms was used instead of the linear polyethylene wax used inExample 5 or 6.9 g of 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexene-3(Example 8) was used instead of di-tert-butyl peroxide used in Example5.

The epoxy group content, melt viscosity, transmittance and haze of eachof the so obtained modified polyethylene waxes were shown in Table 2.

By using the so prepared modified polyethylene waxes, polyethylene/steelplate laminates were prepared in the same manner as described in Example5, and when the peel strength was determined under the conditionsdescribed in Example 5, it was found that the peel strengths of theliminates obtained in Examples 6 to 8 were 2.5 Kg/cm. 1.3 Kg/cm and 1.8Kg/cm. respectively.

EXAMPLE 9 AND COMPARATIVE EXAMPLE 4

A homogeneous transparent melt was prepared under the same conditions asin Example 5 except that 54.8 g of allyl glycidyl ether and 6.0 g ofdi-tert-butyl peroxide were fed at rates of 3.6×10⁻⁴ mole/g.hr and0.30×10⁻⁴ mole/g.hr, respectively (Example 9).

A modified polyethylene wax was prepared in the same manner as inExample 5 except that 54.8 g of allyl glycidyl ether was added at onetime prior to initiation of the reaction and 6.0 g of di-tert-butylperoxide was fed at the same rate as in Example 9 (Comparative Example4). In this comparative run, the melt left after removal of the volatilecomponents in vacuo was opaque, and from results of C₁₃ nuclear magneticresonance spectrum analysis, it was found that the grafted epoxy monomerwas introduced into the polyethylene chain in the state were moleculesof the epoxy monomer were polymerized with one another.

By using the so prepared two modified polyethylene waxes,polyethylene/steel plate laminates were prepared in the same manner asin Example 5, and the peel test was carried out. It was found that thepeel strengths of the products of Example 9 and Comparative Example 4were 0.9 Kg/cm and 0.2 Kg/cm. respectively.

EXAMPLE 10 AND COMPARATIVE EXAMPLE 5

A homogeneous transparent melt was prepared in the same manner as inExample 5 except that 91.2 g of p-isopropenylphenyl glycidyl ether wasused and fed at a rate of 2.0×10⁻⁴ mole/g.hr instead of allyl glycidylether used in Example 5 (Example 10).

The modification reaction was carried out under the same conditions asin Example 5 except that 68.3 g of glycidyl methacrylate was fed at arate of 2.0×10⁻⁴ mole/g.hr instead of allyl glycidyl ether used inExample 5 (Comparative Example 5). While the reaction advanced, a largeamount of a homopolymer of glycidyl methacrylate was formed in the gasphase in the reaction vessel and the homopolymer adhered to the vesselwall. The melt left after removal of the volatile components in vacuowas opaque.

In the same manner as described in Example 5, polyethylene/steel platelaminates were prepared and the peel test was carried out. It was foundthat the peel strengths of the products of Example 10 and ComparativeExample 5 were 1.4 Kg/cm and 0.1 Kg/cm. respectively.

EXAMPLES 11 AND 12

Homogeneous transparent melts were prepared under the same conditions asin Example 5 except that a polyethylene wax prepared according to theFisher method, which had a number average molecular weight of 400, adensity of 0.946 and a melt viscosity of 8 cps (as measured at 140° C.)and contained 13.1 methyl groups and 0.50 internal double bond per 1000carbon atoms (Example 11) or a polyethylene wax prepared by thermaldecomposition of high pressure method polyethylene, which had a numberaverage molecular weight of 3000, a density of 0.924 and a meltviscosity of 240 cps (as measured at 140° C.) and contained 20.7 methylgroups and 4.20 internal double bonds per 1000 carbon atoms (Example 12)was used instead of the linear polyethylene wax used in Example 5.

Polyethylene/steel plate laminates were prepared by using the soobtained modified polyethylene waxes in the same manner as described inExample 5, and the peel test was carried out. It was found that the peelstrengths of the products obtained in Examples 11 and 12 were 0.6 Kg/cmand 0.1 Kg/cm, respectively.

Results obtained in Examples 5 to 12 and Comparative Examples 4 and 5are collectively shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________      Items          Example 5                                                                             Example 6                                                                             Example 7                                                                             Example 8                            __________________________________________________________________________    Synthesis Process of                                                                           Ziegler Ziegler Ziegler Ziegler                              Starting Wax     process process process process                              Number Average Molecular                                                                       1250    2300    1250    1250                                 Weight of Starting Wax                                                        Density of Starting Wax                                                                        0.970   0.970   0.970   0.970                                Number of Methyl Groups                                                                        0       0       20.0    0                                    per 1000 Carbon Atoms                                                         Number of Internal Double                                                                      0.50    0.50    0.50    0.50                                 Bonds per 1000 Carbon Atoms                                                   Melt Viscosity (140° C.) of                                                             70      550     70      70                                   Starting Wax (1)                                                              Epoxy Monomer    allyl glycidyl                                                                        allyl glyci-                                                                          allyl glyci-                                                                          allyl glyci-                                          ether   dyl ether                                                                             dyl ether                                                                             dyl ether                            Initiator        di-tert-butyl                                                                         di-tert-butyl                                                                         di-tert-butyl                                                                         2.5-dimethyl-                                         peroxide                                                                              peroxide                                                                              peroxide                                                                              2.5-di(tert-                                                                  butylperoxy)-                                                                 hexene-3                             Feed Rate (10.sup.-4 mole/g . hr)                                             of Epoxy Monomer 2.0     2.0     2.0     2.0                                  Feed Rate (10.sup.-4 mole/g . hr)                                             of Initiator     0.34    0.34    0.34    0.34                                 __________________________________________________________________________                     Example Comparative                                                                           Example Comparative                            Items          9       Example 4                                                                             10      Example 5                            __________________________________________________________________________    Synthesis Process of                                                                           Ziegler Ziegler Ziegler Ziegler                              Starting Wax     Process process process process                              Number Average Molecular                                                                       1250    1250    1250    1250                                 Weight of Starting Wax                                                        Density of Starting Wax                                                                        0.970   0.970   0.970   0.970                                Number of Methyl Groups                                                                        0       0       0       0                                    per 1000 Carbon Atoms                                                         Number of Internal Double                                                                      0.50    0.50    0.50    0.50                                 Bonds per 1000 Carbon Atoms                                                   Melt Viscosity (140° C.) of                                                             70      70      70      70                                   Starting Wax (1)                                                              Epoxy Monomer    allyl glyci-                                                                          allyl glyci-                                                                          p-isopropenyl                                                                         glycidyl                                              dyl ether                                                                             dyl ether                                                                             phenyl glyci-                                                                         methacrylate                                                          dyl ether                                    Initiator        di-tert-butyl                                                                         di-tert-butyl                                                                         di-tert-butyl                                                                         di-tert-butyl                                         peroxide                                                                              peroxide                                                                              peroxide                                                                              peroxide                             Feed Rate (10.sup.-4 mole/g . hr)                                             of Epoxy Monomer 3.6     added at one                                                                          2.0     2.0                                                           time                                                 Feed Rate (10.sup.-4 mole/g . hr)                                             of Initiator     0.30    0.30    0.34    0.34                                 __________________________________________________________________________      Items               Example 11    Example 12                                __________________________________________________________________________    Synthesis Process of  Fisher        thermal decompo-                          Starting Wax          process       sition process                            Number Average Molecular                                                                            400           3000                                      Weight of Starting Wax                                                        Density of Starting Wax                                                                             0.946         0.924                                     Number of Methyl Groups                                                                             13.1          20.7                                      per 1000 Carbon Atoms                                                         Number of Internal Double                                                                           0.50          4.20                                      Bonds per 1000 Carbon Atoms                                                   Melt Viscosity (140° C.) of                                                                  8             240                                       Starting Wax (1)                                                              Epoxy Monomer         allyl glycidyl                                                                              allyl glycidyl                                                  ether         ether                                     Initiator             di-tert-butyl di-tert-butyl                                                   peroxide      peroxide                                  Feed Rate (10.sup.-4 mole/g . hr)                                             of Epoxy Monomer      2.0           2.0                                       Feed Rate (10.sup.-4 mole/g . hr)                                             of Initiator          0.34          0.34                                      __________________________________________________________________________      Items           Example 5                                                                             Example 6                                                                             Example 7                                                                             Example 8                           __________________________________________________________________________    Number Average Molecular                                                      Weight of Modified Wax                                                                          1800    3500    2000    1800                                Density of Modified Wax                                                                         0.974   0.973   0.922   0.973                               Melt Viscosity (140° C.)                                                                 268     1650    248     256                                 of Modified Wax (1)                                                           Epoxy Group Content                                                                             1.06    0.96    0.94    0.98                                (mg equivalent/g)                                                             Haze (%) of Modified Wax                                                                        1.8     1.7     1.7     1.8                                 Grafting Ratio (%) of                                                                           78.5    71.1    69.0    72.6                                Epoxy Monomer                                                                 180° Peel Strength (Kg/cm)                                             of Polyethylene to Steel Plate                                                                  2.0     2.5     1.3     1.8                                 __________________________________________________________________________                      Example Comparative                                                                           Example Comparative                           Items           9       Example 4                                                                             10      Example 5                           __________________________________________________________________________    Number Average Molecular                                                      Weight of Modified Wax                                                                          1600    1700    2000    2400                                Density of Modified Wax                                                                         0.972   0.970   0.972   0.970                               Melt Viscosity (140°  C.)                                              of Modified Wax (1)                                                                             198     160     197     352                                 Epoxy Group Content                                                           (mg equivalent/g) 0.69    0.50    0.76    0.21                                Haze (%) of Modified Wax                                                                        1.8     3.2     1.6     3.8                                 Grafting Ratio (%) of                                                         Epoxy Monomer     51.1    37.0    61.8    16.0                                180°  Peel Strength (kg/cm)                                            of Polyethylene to Steel Plate                                                                  0.9     0.2     1.4     0.1                                 __________________________________________________________________________      Items               Example 11    Example 12                                __________________________________________________________________________    Number Average Molecular                                                      Weight of Modified Wax                                                                              500           3700                                      Density of Modified Wax                                                                             0.949         0.924                                     Melt Viscosity (140° C.)                                               of Modified Wax (1)   8             1305                                      Epoxy Group Content   0.63          0.15                                      (mg equivalent/g)                                                             Haze (%) of Modified Wax                                                                            2.0           0.8                                       Grafting Ratio (%) of                                                         Epoxy Monomer         46.7          11.1                                      180° Peel Strength (Kg/cm)                                             of Polyethylene to Steel Plate                                                                      0.6           0.1                                       __________________________________________________________________________     Note                                                                          (1) The melt viscosity was measured at 140° C. by a Brookfield         rotational viscometer.                                                   

EXAMPLE 13

In the same manner as described in Example 1, an epoxy-modifiedpolyethylene wax having a number average molecular weight of 1800, anallyl glycidyl ether content of 11.1% by weight (1.154 milligramequivalent/g) and a density of 0.97 was prepared. Then, 10 parts byweight of this allyl glycidyl ether-modified polyethylene wax wasincorporated into 100 parts by weight of a novolak type phenolic resin,and the composition was kneaded for 3 minutes by a hot roll maintainedat 110° C. Then, 50 parts by weight of a wood flour and 12.5 parts byweight of hexamethylene tetramine were added to the composition, and themixture was further kneaded for 2 minutes. Then, the kneaded compositionwas pulverized and passed through a 32-mesh shieve. The flexuralstrength (ASTM D-790) and impact strength (ASTM D-256) of the soobtained phenolic resin composition were measured. It was found that theflexural strength (strength at break) was 692 Kg/cm² and the impactstrength (Izod) was 7.6 ft.lb.

COMPARATIVE EXAMPLE 6

A phenolic resin composition was prepared in the same manner as inExample 13 except that the epoxy-modified polyethylene wax was not addedto the phenolic resin. It was found that the flexural strength (atbreak) and impact strength (Izod) of the so prepared composition was 600Kg/cm² and 48 ft.lb, respectively.

What we claim is:
 1. A thermosetting resinous composition comprising athermosetting resin and 0.5 to 70 parts by weight, per 100 parts byweight of said thermosetting resin, of an epoxy-modified polyolefin waxconsisting of a low-molecular-weight polyolefin grafted, copolymerizedand modified with an epoxy group-containing ethylenically unsaturatedcompound and having a number average molecular weight of from 600 to10,000 and an epoxy equivalent of from 200 to 100,000.
 2. Athermosetting resinous composition as set forth in claim 1 wherein thethermosetting resin is at least one member selected from the groupconsisting of phenolformaldehyde resins, melamine-formaldehyde resins,unreaformaldehyde resins, urethane resins, unsaturated polyester resinsand epoxy resins.
 3. A thermosetting resinous composition as set forthin claim 1 wherein the thermosetting resin is an epoxy resin composed ofa condensate of a polyhydric phenol with an epihalohydrin.
 4. Athermosetting resinous composition as set forth in claim 3 wherein thepolyhydric phenol is bisphenol A or bisphenol F.
 5. A thermosettingresinous composition as set forth in claim 3 wherein the polyhydricphenol is a novolak type phenol-formaldehyde resin.
 6. The thermosettingresinous composition of claim 1 wherein the epoxy group-containing,ethylenically unsaturated compound is a compound of the formula ##STR3##wherein R stands for a monovalent hydrocarbon group containing apolymerizeable ethylenically unsaturated bond.
 7. The thermosettingresinous composition of claim 6 wherein the compound of the formula isallyl glycidyl ether or 2-methylallyl glycidyl ether.
 8. Thethermosetting resinous composition of claim 3 wherein the compound ofthe formula is isopropenylphenyl glycidyl ether or allylphenol glycidylether.
 9. The thermosetting resinous composition of claim 3 wherein theepoxy group-containing, ethylenically unsaturated compound is a compoundof the formula ##STR4## wherein R is a monovalent hydrocarbon grouphaving a polymerizeable ethylenically unsaturated bond, and R' is ahydrogen atom or an alkyl group having up to 4 carbon atoms.
 10. Thethermosetting resinous composition of claim 3 wherein the compound ofthe formula is 2-(allylphenyl) ethylene oxide.